Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS8217213 B2
Publication typeGrant
Application numberUS 12/994,304
PCT numberPCT/US2009/050720
Publication dateJul 10, 2012
Filing dateJul 15, 2009
Priority dateJul 28, 2008
Also published asCN102216215A, CN102216215B, CN103754892A, US20110071329, WO2010014402A1
Publication number12994304, 994304, PCT/2009/50720, PCT/US/2009/050720, PCT/US/2009/50720, PCT/US/9/050720, PCT/US/9/50720, PCT/US2009/050720, PCT/US2009/50720, PCT/US2009050720, PCT/US200950720, PCT/US9/050720, PCT/US9/50720, PCT/US9050720, PCT/US950720, US 8217213 B2, US 8217213B2, US-B2-8217213, US8217213 B2, US8217213B2
InventorsWieslaw J. Roth, Terry E. Helton, Jane C. Cheng, Michael J. Brennan
Original AssigneeExxonmobil Chemical Patents Inc.
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Hydroalkylation of aromatic compounds using EMM-12
US 8217213 B2
Abstract
This disclosure relates to a process for manufacturing a mono-cycloalkyl-substituted aromatic compound, said process comprising contacting a feedstock comprising an aromatic compound and hydrogen under hydroalkylation reaction conditions with a catalyst system comprising a molecular sieve and at least one metal with hydrogenation activity, wherein said molecular sieve has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms.
Images(1)
Previous page
Next page
Claims(20)
1. A process for the hydroalkylation of an aromatic compound comprising the step of contacting the aromatic compound with hydrogen in the presence of a catalyst system comprising a first hydrogenation metal having hydrogenation activity selected from the group consisting of palladium, ruthenium, nickel, and cobalt and an EMM-12 molecular sieve having alkylation activity to produce a cycloalkyl-substituted aromatic compound, wherein said molecular sieve has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms, and non-discrete scattering between about 8.85 to 11.05 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms.
2. The process of claim 1, wherein said molecular sieve further has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms.
3. The process of claim 1, wherein said molecular sieve has a composition involving the molar relationship:

X2O3:(n)YO2,
wherein X is a trivalent element comprising at least one of aluminum, boron, iron and gallium, Y is a tetravalent element comprising at least one of silicon and germanium, and n is at least about 10.
4. The process of claim 3, wherein said molecular sieve, in the as-synthesized form, has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of YO2, as follows:

(0.005-1)M2O:(1-4)R:X2O3 :nYO2
wherein M is an alkali or alkaline earth metal, and R is an organic moiety.
5. The process of claim 3, wherein said n is from about 10 to about 150.
6. The process of claim 3, wherein X is aluminum and Y is silicon.
7. The process sieve of claim 1, wherein said molecular sieve has a collidine adsorption capacity of at least 150 moles/g.
8. The process of claim 1, wherein said aromatic compound is selected from the group consisting of benzene, naphthalene, anthracene, naphthacene, perylene, coronene, phenanthrene, xylene, n-propylbenzene, alpha-methylnaphthalene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, pentaethylbenzene, pentamethylbenzene; 1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene; 1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene; p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalenes; ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene; 2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; 3-methyl-phenanthrene and mixtures thereof.
9. The process of claim 1, wherein said aromatic compound comprises benzene.
10. The process of claim 1, wherein the process is conducted under hydroalkylation reaction conditions comprising a temperature of from about 100° C. to about 400° C., a pressure of from about 500 to about 5000 kPa, a molar ratio of aromatic compound to hydrogen from about 0.01 to about 100, and a feed weight hourly space velocity (WHSV) based on the alkylating agent of from about 0.1 to 500 hr−1.
11. The process of claim 10, wherein said aromatic compound comprises benzene, and said hydroalkylation reaction conditions include a temperature of from about 50° C. to about 350° C., a pressure of from about 100 to about 7000 kPa-a, a molar ratio of aromatic compound to hydrogen of from about 0.01 to about 100, and a feed weight hourly space velocity (WHSV) of from about 0.01 to 100 hr−1.
12. The process of claim 10, wherein said aromatic compound comprises benzene and said hydroalkylation reaction conditions include a temperature of from about 10° C. to about 250° C., a pressure of from about 100 to about 3000 kPa-a, a molar ratio of hydrogen to benzene of from about .0.4 to about 0.9 and a feed weight hourly space velocity (WHSV) based on benzene of from about 0.01 to 250 hr−1.
13. The process of claim 1, wherein a monocycloalkyl-substituted aromatic compound and a dicycloalkyl-substituted compound are produced at a ratio of monocycloalkyl-substituted aromatic compound to dicycloalkyl-substituted compound of greater than about 10.
14. The process of claim 1, wherein said aromatic compound comprises benzene and wherein cyclohexylbenzene and dicyclohexylbenzene are produced at a ratio of cyclohexylbenzene to dicyclohexylbenzene of greater than about 10.
15. The process of claim 1, wherein at least a portion of the first hydrogenation metal is supported on an inorganic oxide different from the molecular sieve.
16. The process of claim 15, wherein the first hydrogenation metal is applied to the inorganic oxide before the inorganic oxide is composited with the molecular sieve.
17. The process of claim 1, wherein the catalyst system also contains a second hydrogenation metal, different from the first hydrogenation metal, and the second hydrogenation metal is selected from zinc, tin, nickel and cobalt.
18. A process for the hydroalkylation of an aromatic compound, comprising:
a hydroalkylation step comprising contacting the aromatic compound with hydrogen in the presence of a catalyst system comprising a first hydrogenation metal having hydrogenation activity selected from the group consisting of palladium, ruthenium, nickel, and cobalt and an EMM-12 molecular sieve having alkylation activity to produce a mono-cycloalkyl-substituted aromatic compound and a di-cycloalkyl-substituted aromatic compound, wherein said molecular sieve has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms, and non-discrete scattering between about 8.85 to 11.05 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms; and
a transalkylating step comprising contacting the di-cycloalkyl-substituted aromatic compound with additional aromatic compound in the presence of a transalkylation catalyst to produce additional mono-cycloalkyl-substituted aromatic compound.
19. The process of claim 18, wherein the hydroalkylation and transalkylation steps are effected in separate reactors.
20. The process of claim 19, wherein the transalkylation catalyst comprises a molecular sieve and the transalkylation step comprises at least partial liquid phase conditions comprising a temperature of about 100° to about 300° C., a pressure of about 800 to 3500 kPa, a weight hourly space velocity of about 1 to about 10 hr−1 on total feed, a mono-cycloalkyl-substituted aromatic compound/di-cycloalkyl-substituted aromatic compound weight ratio of about 1:1 to about 5:1, or a combination thereof.
Description
PRIORITY CLAIM

This application claims the benefit of prior U.S. Provisional Application Ser. No. 61/084,166 filed Jul. 28, 2008, and International Patent Cooperation Treaty Application No. PCT/US2009/050720, filed Jul. 15, 2009, both of which are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

The present disclosure relates to a process for the hydroalkylation of aromatic compounds and particularly to a process for the hydroalkylation of benzene to produce cyclohexylbenzene, using a molecular sieve composition designated as EMM-12 which is an MCM-22 family material having unique XRD features.

BACKGROUND OF THIS DISCLOSURE

Molecular sieve materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Molecular sieves that find application in catalysis include any of the naturally occurring or synthetic crystalline molecular sieves. Examples of these zeolites include large pore zeolites, intermediate pore size zeolites, and small pore zeolites. These zeolites and their isotypes are described in “Atlas of Zeolite Framework Types”, eds. W. H. Meier, D. H. Olson and Ch. Baerlocher, Elsevier, Fifth Edition, 2001, which is hereby incorporated by reference. A large pore zeolite generally has a pore size of at least about 7 Å and includes LTL, VFI, MAZ, FAU, OFF, *BEA, and MOR framework type zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of large pore zeolites include mazzite, offretite, zeolite L, VPI-5, zeolite Y, zeolite X, omega, and Beta. An intermediate pore size zeolite generally has a pore size from about 5 Å to less than about 7 Å and includes, for example, MFI, MEL, EUO, MTT, MFS, AEL, AFO, HEU, FER, MWW, and TON framework type zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of intermediate pore size zeolites include ZSM-5, ZSM-11, ZSM-22, MCM-22, silicalite 1, and silicalite 2. A small pore size zeolite has a pore size from about 3 Å to less than about 5.0 Å and includes, for example, CHA, ERI, KFI, LEV, SOD, and LTA framework type zeolites (IUPAC Commission of Zeolite Nomenclature). Examples of small pore zeolites include ZK-4, ZSM-2, SAPO-34, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, zeolite A, chabazite, zeolite T, gmelinite, ALPO-17, and clinoptilolite.

U.S. Pat. No. 4,439,409 refers to a crystalline molecular sieve composition of matter named PSH-3 and its synthesis from a reaction mixture for hydrothermal reaction containing hexamethyleneimine, an organic compound which acts as directing agent for synthesis of the MCM-56 (U.S. Pat. No. 5,362,697). Hexamethyleneimine is also taught for use in synthesis of crystalline molecular sieves MCM-22 (U.S. Pat. No. 4,954,325) and MCM-49 (U.S. Pat. No. 5,236,575). A molecular sieve composition of matter referred to as zeolite SSZ-25 (U.S. Pat. No. 4,826,667) is synthesized from a reaction mixture for hydrothermal reaction containing an adamantane quaternary ammonium ion. U.S. Pat. No. 6,077,498 refers to a crystalline molecular sieve composition of matter named ITQ-1 and its synthesis from a reaction mixture for hydrothermal reaction containing one or a plurality of organic additives.

U.S. patent application Ser. No. 11/823,129 discloses a molecular sieve composition designated as EMM-10-P, having, in its as-synthesized form, an X-ray diffraction pattern including d-spacing maxima at 13.18±0.25 and 12.33±0.23 Angstroms, wherein the peak intensity of the d-spacing maximum at 13.18±0.25 Angstroms is at least as great as 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms. U.S. patent application Ser. No. 11/824,742 discloses a molecular sieve composition designated as EMM-10, in its ammonium exchanged form or in its calcined form, comprising unit cells with MWW topology, said crystalline molecular sieve is characterized by diffraction streaking from the unit cell arrangement in the c direction. The crystalline molecular sieve is further characterized by the arced hk0 patterns of electron diffraction pattern. The crystalline molecular sieve is further characterized by the streaks in the electron diffraction pattern along the c* direction. U.S. patent application Ser. No. 11/827,953 discloses a crystalline MCM-22 family molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern including a peak at d-spacing maximum of 12.33±0.23 Angstroms, a distinguishable peak at a d-spacing maximum between 12.57 to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximum between 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacing maximum between 12.57 to about 14.17 Angstroms is less than 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms.

The term “MCM-22 family material” (or “material of the MCM-22 family” or “molecular sieve of the MCM-22 family”), as used herein, includes:

  • (i) molecular sieves made from a common first degree crystalline building block “unit cell having the MWW framework topology”. A unit cell is a spatial arrangement of atoms which is tiled in three-dimensional space to describe the crystal as described in the “Atlas of Zeolite Framework Types”, Fifth edition, 2001, the entire content of which is incorporated as reference;
  • (ii) molecular sieves made from a common second degree building block, a 2-dimensional tiling of such MWW framework type unit cells, forming a “monolayer of one unit cell thickness”, preferably one c-unit cell thickness;
  • (iii) molecular sieves made from common second degree building blocks, “layers of one or more than one unit cell thickness”, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thick of unit cells having the MWW framework topology. The stacking of such second degree building blocks can be in a regular fashion, an irregular fashion, a random fashion, or any combination thereof; or
  • (iv) molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topology.

The MCM-22 family materials are characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22 family materials may also be characterized by having an X-ray diffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized). The X-ray diffraction data used to characterize the molecular sieve are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system. Materials belong to the MCM-22 family include MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described in European Patent No. 0293032), ITQ-1 (described in U.S. Pat. No. 6,077,498), ITQ-2 (described in International Patent Publication No. WO97/17290), ITQ-30 (described in International Patent Publication No. WO2005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat. No. 5,362,697), EMM-10-P (described in U.S. patent application Ser. No. 11/823,129) and EMM-10 (described in U.S. patent application Ser. No. 11/824,742). The entire contents of the patents are incorporated herein by reference.

It is to be appreciated the MCM-22 family molecular sieves described above are distinguished from conventional large pore zeolite alkylation catalysts, such as mordenite, in that the MCM-22 materials have 12-ring surface pockets which do not communicate with the 10-ring internal pore system of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWW topology are multi-layered materials which have two pore systems arising from the presence of both 10 and 12 membered rings. The Atlas of Zeolite Framework Types classes five differently named materials as having this same topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in a variety of hydrocarbon conversion processes. Examples of MCM-22 family molecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, and ERB-1. Such molecular sieves are useful for alkylation of aromatic compounds. For example, U.S. Pat. No. 6,936,744 discloses a process for producing a mono-alkylaromatic compound, particularly cumene, comprising the step of contacting a polyalkylated aromatic compound with an alkylatable aromatic compound under at least partial liquid phase conditions and in the presence of a transalkylation catalyst to produce the mono-alkylaromatic compound, wherein the transalkylation catalyst comprises a mixture of at least two different crystalline molecular sieves, wherein each of the molecular sieves is selected from zeolite beta, zeolite Y, mordenite and a material having an X-ray diffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms.

A report by J. Ruan, P. Wu, B. Slater, L. Wu, J. Xiao, Y. Liu, M. He, O. Terasaki at the 15 IZA Conference in Beijing in 2007 disclosed ISE-MWW and ISE-FER materials, the former made from MCM-22-P material as starting material. U.S. Patent Application Publication 2005/0158238 to Tatsumi et al. disclosed MWW type zeolite substance. U.S. Patent Application Publication 2004/0092757 to Oguchi et al. disclosed crystalline MWW type titanosilicate catalyst. A report by W. Fan, P. Wu, S, Namba, and T. Tatsumi (J. Catalyst 243 (2006) 183-191) disclosed a new titanosilicate molecular sieve with the structure analogous to MWW-type lamellar precursor. J. Ruan, P. Wu B. Slater and O. Terasaki disclosed detailed structure of Ti—YNU-1 (Angew. Chem. Int. Ed., 2005, 44, 6719) similar to ISE-MWW. It is known that crystal morphology, size and aggregation/agglomeration, or new x-ray diffraction can affect catalyst behavior, especially regarding catalyst activity and stability.

It has been known for many years that cyclohexylbenzene can be produced from benzene by the process of hydroalkylation or reductive alkylation. In this process, benzene is heated with hydrogen in the presence of a catalyst such that the benzene undergoes partial hydrogenation to produce cyclohexene which then alkylates the benzene starting material. Thus U.S. Pat. Nos. 4,094,918 and 4,177,165 disclose hydroalkylation of aromatic compounds over catalysts which comprise nickel- and rare earth-treated zeolites and a palladium promoter. Similarly, U.S. Pat. Nos. 4,122,125 and 4,206,082 disclose the use of ruthenium and nickel compounds supported on rare earth-treated zeolites as aromatic hydroalkylation catalysts. The zeolites employed in these prior art processes are zeolites X and Y. In addition, U.S. Pat. No. 5,053,571 proposes the use of ruthenium and nickel supported on zeolite beta as the aromatic hydroalkylation catalyst. However, these earlier proposals for the hydroalkylation of benzene suffer from the problems that the selectivity to cyclohexylbenzene is low, particularly at economically viable benzene conversion rates, and that large quantities of unwanted by-products, particularly cyclohexane and methylcyclopentane, are produced.

More recently, U.S. Pat. No. 6,037,513 has disclosed that cyclohexylbenzene selectivity in the hydroalkylation of benzene can be improved by contacting the benzene and hydrogen with a bifunctional catalyst comprising at least one hydrogenation metal and a molecular sieve of the MCM-22 family. The hydrogenation metal is preferably selected from palladium, ruthenium, nickel, cobalt and mixtures thereof and the contacting step is conducted at a temperature of about 50 to 350° C., a pressure of about 100 to 7000 kPa, a benzene to hydrogen molar ratio of about 0.01 to 100 and a WHSV of about 0.01 to 100. The '513 patent discloses that the resultant cyclohexylbenzene can then be oxidized to the corresponding hydroperoxide and the peroxide decomposed to the desired phenol and cyclohexanone.

According to the present invention, it has now been found the hydroalkylation of an aromatic compound over a bifunctional catalyst comprising a EMM-12 zeolite and at least one hydrogenation metal yields a favorable ratio of the produced monocycloalkyl-substituted aromatic compound to the produced di-cycloalkyl-substituted aromatic compound. Although the di-cycloalkyl-substituted aromatic compound can be transalkylated back to corresponding mono-cycloalkyl-substituted aromatic compound, the cost of transalkylation is not insignificant.

There is, therefore, a need for a new process of producing cycloalkyl-substituted aromatic compounds, especially mono-cylcoalkyl-substituted aromatic compounds, with crystalline molecular sieve.

SUMMARY OF THIS DISCLOSURE

In some embodiments, this disclosure relates to a hydroalkylation process of producing mono-cycloalkyl-substituted aromatic compounds using a catalyst system comprising a molecular sieve and at least one hydrogenation metal having hydrogenation activity, wherein the molecular sieve has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms (˜6.15-7.05 deg 2-θ Cu Kα), a d-spacing maximum in the range of 12.1 to 12.56 Angstroms (˜7.3-7.05 deg 2-θ Cu Kα), and non-discrete scattering between about 8.66 to 12.0 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg 2-θ Cu Kα) and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ) but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg 2-θ Cu Kα) and in the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ Cu Kα).

In other embodiments, this disclosure relates to a hydroalkylation process of producing mono-cycloalkyl-substituted aromatic compounds using a catalyst comprising a molecular sieve and at least one hydrogenation metal having hydrogenation activity, wherein the molecular sieve has, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at d-spacing maxima at 13.5±0.25, 12.33±0.23, and non-discrete scattering between about 8.66 to 12.0 Angstroms or exhibit a valley in between the peaks at 11.05±0.3 and 9.31±0.3 Angstroms but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

In yet other embodiments, the aromatic compound is benzene and the corresponding mono-cycloalkyl-substituted aromatic compound is cyclohexylbenzene.

In yet other embodiments, the process of this disclosure comprises contacting an aromatic compound with hydrogen in the presence of a catalyst system comprising (i) a molecular sieve; (ii) an inorganic oxide different from the molecular sieve; and (iii) at least one hydrogenation metal under hydroalkylation conditions to form mono-cycloalkyl-substituted alkylaromatic compounds.

In a further embodiment, this disclosure relates to a catalyst system comprising (i) a molecular sieve having, in its as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms, and non-discrete scattering between about 8.85 to 11.05 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms; (ii) an inorganic oxide different from said molecular sieve; and (iii) at least one hydrogenation metal wherein at least a portion of the hydrogenation metal is supported on the inorganic oxide in (ii).

These and other facets of the present invention shall become apparent from the following detailed description, FIGURES, and appended claims.

BRIEF DESCRIPTION OF THE FIGURE

FIG. 1 shows the XRD pattern between 5 to 11 degree 2-θ of Example 1.

DETAILED DESCRIPTION Introduction

Described herein is a process for the hydroalkylation of aromatic compounds, particularly benzene, to produce cycloalkyl-substituted aromatic compounds. Insofar as the hydroalkylation step produces di-cycloalkyl-substituted aromatic compounds (e.g. dicyclohexylbenzene) in addition to the desired mono-cycloalkyl-substituted aromatic compound product (e.g. mono-cyclohexylbenzene), the process can include the further step of transalkylating the di-cycloalkyl-substituted aromatic compounds with additional aromatic compounds (e.g. benzene) to produce additional mono-cycloalkyl-substituted aromatic compound product.

All patents, patent applications, test procedures (such as ASTM methods, UL methods, and the like), priority documents, articles, publications, manuals, and other documents cited herein are fully incorporated by reference to the extent such disclosure is not inconsistent with the present invention and for all jurisdictions in which such incorporation is permitted.

When numerical lower limits and numerical upper limits are listed herein, ranges from any lower limit to any upper limit are contemplated. While the illustrative embodiments of the disclosure have been described with particularity, it will be understood that various other modifications will be apparent to and can be readily made by those skilled in the art without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the scope of the claims appended hereto be limited to the examples and descriptions set forth herein but rather that the claims be construed as encompassing all the features of patentable novelty which reside in the present disclosure, including all features which would be treated as equivalents thereof by those skilled in the art to which the disclosure pertains.

As used in this specification, the term “framework type” is used in the sense described in the “Atlas of Zeolite Framework Types,” 2001.

As used herein, the numbering scheme for the Periodic Table Groups is used as in Chemical and Engineering News, 63(5), 27 (1985).

The present invention encompasses the hydroalkylation of any aromatic compounds, however, the details of benzene alkylation are presented below as a specific example. It is to be understood that all embodiments useful for benzene hydroalkylation are also useful in the hydroalkylation of other aromatic compounds.

Hydroalkylation Process

The term “aromatic” in reference to the aromatic compounds which may be useful as feedstock herein is to be understood in accordance with its art-recognized scope. This includes alkyl substituted and unsubstituted mono- and polynuclear compounds. Compounds of an aromatic character that possess a heteroatom may also be useful provided sufficient catalytic activity is maintained under the reaction conditions selected.

Substituted aromatic compounds that can be hydroalkylated herein must possess at least one hydrogen atom directly bonded to the aromatic nucleus. The aromatic rings can be substituted with one or more alkyl, aryl, alkaryl, alkoxy, aryloxy, cycloalkyl, halide, and/or other groups that do not interfere with the hydroalkylation reaction.

Suitable aromatic compounds include benzene, naphthalene, anthracene, naphthacene, perylene, coronene, and phenanthrene, with benzene being preferred.

In another embodiment, the aromatic compound is selected from the group consisting of benzene, naphthalene, anthracene, naphthacene, perylene, coronene, phenanthrene, xylene, n-propylbenzene, alpha-methylnaphthalene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, pentaethylbenzene, pentamethylbenzene; 1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene; 1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene; p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene; m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalenes; ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene; 2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; 3-methyl-phenanthrene and mixtures thereof.

The first step in the present process comprises contacting an aromatic compound (e.g. benzene) with hydrogen under hydroalkylation conditions in the presence of a hydroalkylation catalyst whereby the in the case of benzene, the aromatic compound undergoes the following reaction to produce cyclohexylbenzene (CHB):

In the case of benzene hydroalkylation, competing reactions include the complete saturation of the benzene to produce cyclohexane, dialkylation to produce dicyclohexylbenzene and reorganization/alkylation reactions to produce impurities, such as methylcyclopentylbenzene (MCPB). Although dicyclohexylbenzene can be transalkylated to produce additional CHB product, conversion to cyclohexane represents loss of valuable feed, whereas impurities such as methylcyclopentylbenzene (MCPB) are particularly undesirable since the boiling point of MCPB is very close to that of CHB so that it is very difficult to separate MCPB from CHB. It is therefore important to minimize the production of MCPB impurity in the hydroalkylation reaction.

Preferably, the hydroalkylation reaction yields a ratio of mono-cycloalkyl-substituted aromatic compound to di-cycloalkyl-substituted aromatic compound from greater than about 10, about 15, about 20, about 25, about 40, about 50, about 60, about 70, and about 80. For example, in the case of benzene hydroalkylation, the reaction yields a ratio of cyclohexylbenzene to dicyclohexylbenzene of from greater than about 10, about 15, about 20, about 25, about 40, about 50, about 60, about 70, and about 80.

Any commercially available benzene feed can be used in the hydroalkylation step, but preferably the benzene has a purity level of at least 99 wt %. Similarly, although the source of hydrogen is not critical, it is generally desirable that the hydrogen is at least 99 wt % pure.

Preferably, the total feed to the hydroalkylation step contains less than 1000 ppm, such as less than 500 ppm, for example less than 100 ppm, water. Preferably, the total feed typically contains less than 100 ppm, such as less than 30 ppm, for example less than 3 ppm, sulfur. Preferably, the total feed contains less than 10 ppm, such as less than 1 ppm, for example less than 0.1 ppm, nitrogen. In a particularly preferred embodiment at least two, and preferably all three of the above mentioned preferred levels for water, sulfur and nitrogen are achieved.

The hydroalkylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers. In addition, the hydroalkylation reaction can be conducted in a single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages. Irrespective of whether the hydrogen is fed to the reaction continuously or in stages, it is important that the ratio of the total number of moles of hydrogen fed to the reaction to the number of moles of benzene fed to the reaction is between 0.4 and 0.9:1, such as between about 0.5 and about 0.8:1, for example between about 0.6 and about 0.7:1.

Suitable temperatures for conducting the hydroalkylation reaction are between about 100° C. and about 400° C., such as between about 125° C. and about 250° C. Suitable reaction pressures are between about 100 and about 7,000 kPaa, such as between about 500 and about 5,000 kPa-a. Suitable feed weight hourly space velocity (WHSV) based on benzene of from about 0.01 to 250 hr−1, from about 0.1 to about 50 hr−1, from about 0.1 to about 5.0 hr−1, and from about 0.2 to about 1.5 hr−1.

The catalyst employed in the hydroalkylation reaction is a bifunctional catalyst comprising a molecular sieve of EMM-12 described herein and at least one hydrogenation metal.

Any known hydrogenation metal can be employed in the present hydroalkylation catalyst although suitable metals for the first hydrogenation metal include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous. Generally, the amount of hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt %, such as between about 0.1 and about 5 wt %, of the catalyst. In one embodiment, where the EMM-12 is an aluminosilicate, the amount of hydrogenation metal present is such that the molar ratio of the aluminum in the molecular sieve to the hydrogenation metal is from about 1.5 to about 1500, for example from about 75 to about 750, such as from about 100 to about 300.

The catalyst preferably contains a second hydrogenation metal component, in addition to and different from the hydrogenation metal, which acts to promote the hydrogenation function of the catalyst. Suitable second hydrogenation metal components are selected from zinc, tin, nickel, cobalt and mixtures thereof. Again, the amount of second metal component present in the catalyst may vary significantly but preferably the amount of the second hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt %, such as between about 0.1 and about 5 wt %, of the catalyst.

The hydrogenation metal may be directly supported on the EMM-12 molecular sieve by, for example, impregnation or ion exchange. However, in a more preferred embodiment, at least a portion, for example at least 50 wt %, at least 75 wt %, and generally substantially all of the at least one hydrogenation metal is supported on an inorganic oxide separate from but composited with the molecular sieve. In particular, it is found that by supporting the hydrogenation metal on the inorganic oxide, the activity of the catalyst and its selectivity to cyclohexylbenzene and dicyclohexylbenzene are increased as compared with an equivalent catalyst in which the hydrogenation metal is supported on the molecular sieve.

The inorganic oxide employed in such a composite hydroalkylation catalyst is not narrowly defined provided it is stable and inert under the conditions of the hydroalkylation reaction. Suitable inorganic oxides include oxides of Groups 2, 4, 13 and 14 of the Periodic Table of Elements, such as alumina and/or titania and/or zirconia. As used herein, the numbering scheme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), 27 (1985). When the catalyst system comprises a composite of the molecular sieve and the inorganic oxide that is different from the molecular sieve, these two components are conveniently present in a weight ratio in the range 90:10 to 10:90, such as 80:20 to 20:80, for example 70:30 to 30:70 or 60:40 to 40:60.

In the above-mentioned preferred embodiment, the hydrogenation metal is deposited on the inorganic oxide, conveniently by impregnation, before the metal-containing inorganic oxide is composited with the molecular sieve. Typically, the catalyst composite is produced by co-pelletization, in which a mixture of the molecular sieve and the metal-containing inorganic oxide are formed into pellets at high pressure (generally about 350 to about 350,000 kPa), or by co-extrusion, in which a slurry of the molecular sieve and the metal-containing inorganic oxide, optionally together with a separate binder, are forced through a die. If necessary, additional hydrogenation metal can subsequently be deposited on the resultant catalyst composite.

Suitable binder materials include synthetic or naturally occurring substances as well as inorganic materials such as clay, silica and/or metal oxides. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.

Although the hydroalkylation step is highly selective towards mono-cycloalkyl-substituted aromatic compound products (e.g. cyclohexylbenzene), the effluent from the hydroalkylation reaction will normally contain some dialkylated products, as well as unreacted aromatic feed and the desired monoalkylated species. The unreacted aromatic feed is normally recovered by distillation and recycled to the alkylation reactor. In the case of benzene hydroalkylation, for example, the bottoms from the distillation are further distilled to separate the monocyclohexylbenzene product from any dicyclohexylbenzene and other heavies. Depending on the amount of dicyclohexylbenzene present in the reaction effluent, it may be desirable to transalkylate the dicyclohexylbenzene with additional benzene to maximize the production of the desired monoalkylated species.

Transalkylation with additional aromatic compound (e.g. benzene) is typically effected in a transalkylation reactor, separate from the hydroalkylation reactor, over a suitable transalkylation catalyst, such as a molecular sieve of the MCM-22 family, zeolite beta, MCM-68 (see U.S. Pat. No. 6,014,018), zeolite Y or mordenite. The transalkylation reaction is typically conducted under at least partial liquid phase conditions, which suitably include a temperature of about 100 to about 300° C. and/or a pressure of about 800 to about 3500 kPa and/or a weight hourly space velocity of about 1 to about 10 hr−1 on total feed and/or a mono-cycloalkyl-substituted aromatic compound/di-cycloalkyl-substituted aromatic compound weight ratio about of 1:1 to about 5:1.

X-Ray Powder Diffraction Pattern for EMM-12

The interplanar spacings, d's, were calculated in Angstrom units (Å), and the relative intensities of the lines, I/Io, where the intensity of the strongest line above background, Io, is counted as 100, were derived with the use of a profile fitting routine (or second derivative algorithm). The intensities are uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols VS=very strong (greater than 60 to 100), S=strong (greater than 40 to 60), M=medium (greater than 20 to 40) and W=weak (0 to 20). It should be understood that diffraction data listed as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in the structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, and thermal and/or hydrothermal history. Other changes in diffraction patterns can be indicative of important differences between materials, which is the case for comparing MCM-22 with similar materials, e.g., MCM-49, MCM-56, and PSH-3.

The interplanar spacings, d's, were considered broad if they exhibited peak width of about 1.5° or more at half height determined as 50% intensity value from the maximum to the baseline.

The term “XRD distinguishable peak” as used herein is defined as XRD peak with clearly defined peak maximum, which is at least two times of the average background noise level.

The term “non-discrete” peaks (also “unresolved” peaks) in XRD as used herein means peaks having a monotonic profile in-between them (successive points either consistently increasing (or staying even) or decreasing (or staying even) within noise).

The term “discrete” peaks (also “resolved” peaks) in XRD as used herein means XRD peak(s) which are not non-discrete (unresolved).

FIG. 1 graphically demonstrates the XRD pattern between 5 to 11 degree 2-θ of the product of Example 1. The measured intensity corrected for background at the lowest point between d-spacing maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms, represented as B, is the distance between the lowest point (point a) and the point (point b) on the line of the background correction line at the same XRD d-spacing of the lowest point (point a). The distance between the point b and the point (point c) on the line connecting d-spacing maxima in the range of 10.14 to 12.0 Angstroms and in the range from 8.66 to 10.13 Angstroms at the same XRD d-spacing of the lowest point is represented as A.

Composition Matter of EMM-12

In some embodiments, the composition matter of EMM-12 has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks having a d-spacing maximum in the range of 14.17 to 12.57 Angstroms (˜6.15-7.05 deg 2-θ Cu Kα), such as, at 13.5±0.25, a d-spacing maximum in the range of 12.1 to 12.56 Angstroms (˜7.3-7.05 deg 2-θ), such as, 12.33±0.23, and non-discrete scattering between about 8.66 to 12.0 Angstroms or exhibit a valley in between the peaks having a d-spacing maximum in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg 2-θ), such as, at 11.05±0.3, and a d-spacing maximum in the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ), such as, at 9.31±0.3 Angstroms, with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting d-spacing maximum in the range of 10.14 to 12.0 Angstroms (8.7-7.35 deg 2-θ) and d-spacing maximum in the range from 8.66 to 10.13 Angstroms (10.2-8.7 deg 2-θ).

In some embodiments, the composition matter of EMM-12 has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at d-spacing maxima at 13.5±0.25, 12.33±0.23, and non-discrete scattering between about 8.85 to 11.05 Angstroms or exhibit a valley in between the peaks at 11.05±0.3 and 9.31±0.3 Angstroms but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

In further embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at d-spacing maxima at 3.57±0.06 and 3.43±0.06 Angstroms. In yet further embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peak at d-spacing maximum at 6.9±0.15 Angstroms. In yet further embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peak at d-spacing maximum at 3.96±0.08 Angstroms.

In other embodiments, the composition matter of EMM-12 has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at d-spacing maxima and relative intensities at 13.5±0.25 (M-VS), 12.33±0.23 (M-VS), and non-discrete scattering between about 8.85 to 11.05 Angstroms (W—S) or exhibit a valley in between the peaks at 11.05±0.18 (W—S) and 9.31±0.13 (W—S) Angstroms but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

TABLE 1
Interplanar d-Spacing (Å) Relative Intensity, I/Io × 100
 14.17 > d > 12.57 M-VS
12.56 > d > 12.1 M-VS
 12.0 > d > 10.14 W-S
10.13 > d > 8.66 W-S
 6.9 ± 0.15 W-M, broad
3.96 ± 0.08 W-VS, broad
3.57 ± 0.06 W-M
3.43 ± 0.06 M-VS

In other embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peaks at d-spacing maxima at 3.57±0.06 (W-M) and 3.43±0.06 (M-VS) Angstroms. In yet further embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peak at d-spacing maximum at 6.9±0.15 Angstroms (W-M, broad). In yet further embodiments, the composition matter of EMM-12 further has, in as-synthesized form and in calcined form, an X-ray diffraction pattern including peak at d-spacing maximum at 3.96±0.08 Angstroms (W—VS, broad).

In some preferred embodiments, the X-ray diffraction pattern of the crystalline molecular sieve EMM-12 further has peaks at d-spacing maxima and intensities listed in Table 2.

In some embodiments, the X-ray diffraction pattern of the crystalline molecular sieve EMM-12 of this disclosure further includes a d-spacing maximum at 28±2 Angstroms.

In some embodiments, the EMM-12 exhibits an extraordinary high collidine number of greater than 150 μmoles/g, preferably greater than 200 μmoles/g, more preferably greater than 250 μmoles/g, even more preferably greater than 300 μmoles/g, and most preferably greater than 350 μmoles/g, compared for up to about 200 μmoles/g for EMM-10 and 120 μmoles/g for MCM-22.

Chemical Composition of as-Synthesized EMM-12 and Calcined EMM-12

The as-synthesized EMM-12 molecular sieve material of this disclosure may have a composition, in terms of mole ratios of oxides:

    • YO2/X2O3 in the range of 10 to infinity or in the range of 10 to 50;
    • M/X2O3 in the range of 0.005-0.1; and
    • R/X2O3 in the range of 1-4.

The calcined EMM-12 molecular sieve material of this disclosure may be prepared by calcining as-synthesized EMM-12 under calcination conditions to remove at least the majority of the organic template R from the as-synthesized EMM-12.

Process of Making EMM-12

In some embodiments, this disclosure relates to a method of manufacturing an as-synthesized crystalline molecular sieve EMM-12, the method comprising the steps of:

    • (a) providing a mixture comprising EMM-10-P family composition and acidic composition, optionally a spacing agent;
    • (b) treating the mixture at treatment conditions to form a product comprising as-synthesized EMM-12; and
    • (c) recovering the acid treated crystalline molecular sieve.

In some preferred embodiments, the as-synthesized EMM-12 is made by a process comprising:

    • (1) providing a mixture comprising EMM-10-P having Si/Al2 in the range from 10-infinity, preferable from about 10 to 150, and acidic composition comprising at least one of nitric acid, sulfuric acid, hydrochloric acid; oxalic acid, wherein said acid has a concentration of less than or equal to 10 N, preferably less than 1N, optionally a spacing agent comprising at least one of dimethyldiethoxy silane, diethyldiethoxy silane, and tetraethyl silane (TEOS), preferable TEOS; and
    • (2) treating the mixture of step (1) to treatment conditions, wherein the treatment conditions comprise a temperature in the range of 50-170° C. for a time in the range of 1-24 hrs, optionally with a stirring speed in the range of 0-1000 RPM.

The mixture of step (a) comprises EMM-10-P family composition, acidic composition, and optionally a spacing agent, wherein the weight ratio of the solid content of the EMM-10-P family composition over the acidic composition and the weight ratio of the spacing agent over the solid content of the EMM-10-P family composition are listed in the following table (Table 2). Useful and preferred ranges of the treatment temperature and treatment time are also listed in Table 2.

TABLE 2
Most preferred
Useful range Preferred range range
Solid content (wt) 0.001-1000  0.01-100   0.1-10
Acidiccomposition
Spacing agent (wt) 0-2 0-1  0.01-0.5
Solid content (wt)
Acid concentration (N) 0.001-10   0.001-5    0.01-2  
Temperature (° C.)  25-250 50-200  90-170
Time (hr) 0.01-240  1-48  1-24

The following solid content over acidic composition weight ratios are useful lower limits: 0.001, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100 and 500. The following solid content over acidic composition weight ratios are useful upper limits: 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 50, 100, 500 and 1000. The solid content over acidic composition weight ratio falls in a range between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits, so long as the lower limit is less than or equal to the upper limit. The solid content over acidic composition weight ratio may be present in an amount ranging from 0.01 to 100 in one embodiment, alternatively 0.1 to 10, alternatively 0.1 to 5.

The following ratios are useful lower spacing agent over solid content weight ratio limits: 0, 0.001, 0.01, 0.05, 0.1, 0.5, 1, and 1.5. The following ratios are useful upper spacing agent over solid content weight ratio limits: 0.001, 0.01, 0.05, 0.1, 0.5, 1, 1.5, and 2. The spacing agent over solid content weight ratio falls in a range between any one of the above-mentioned lower spacing agent over solid content weight ratio limits and any one of the above-mentioned upper spacing agent over solid content weight ratio limits, so long as the lower spacing agent over solid content weight ratio limit is less than or equal to the upper spacing agent over solid content weight ratio limit. The spacing over solid content weight ratio may be present in an amount ranging from 0 to 2 in one embodiment, alternatively 0 to 1, and alternatively 0.1 to 0.5.

The following temperatures (° C.) are useful lower treatment temperature limits: 25, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, and 200. The following temperatures (° C.) are useful upper treatment temperature limits: 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, and 250. The treatment temperature (° C.) falls in a range between any one of the above-mentioned lower treatment temperature limits and any one of the above-mentioned upper treatment temperature limits, so long as the lower treatment temperature limit is less than or equal to the upper treatment temperature limit. The treatment temperature may be present in an amount ranging from 25° C. to 250° C. in one embodiment, alternatively 70° C. to 200° C., and alternatively 90° C. to 170° C.

The following times (hr) are useful lower time limits for treatment: 0.01, 1, 5, 10, 20, 30, 50, 100, and 150. The following time (hr) are useful upper time limits for treatment: 1, 5, 10, 20, 40, 50, 70, 100, 150, 200, and 240. The time (hr) for treatment falls in a range between any one of the above-mentioned lower time limits for treatment and any one of the above-mentioned upper time limits for treatment, so long as the lower time limit for treatment is less than or equal to the upper time limit for treatment. The time for treatment may be present in an amount ranging from 1 to 100 in one embodiment, alternatively 1 to 48, and alternatively 1 to 24.

(1) EMM-10-P Family Composition

EMM-10-P family composition as used herein comprises at least one of EMM-10-P composition disclosed in U.S. patent application Ser. No. 11/823,129 (its entirety of which is enclosed herein by reference) and as-synthesized MCM-22 family molecular sieve composition disclosed in U.S. patent application Ser. No. 11/827,953 (its entirety of which is enclosed herein by reference).

The EMM-10-P composition relates to a crystalline molecular sieve, designated as EMM-10-P, having, in its as-synthesized form, an X-ray diffraction pattern including d-spacing maxima at 13.18±0.25 and 12.33±0.23 Angstroms, wherein the peak intensity of the d-spacing maximum at 13.18±0.25 Angstroms is at least as great as 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms. In addition, the X-ray diffraction pattern of the EMM-10-P molecular sieve further includes two XRD distinguishable peaks with d-spacing maxima at 11.06±0.18 and 9.25±0.13 Angstroms, wherein the peak intensity of the d-spacing maximum at 11.06±0.18 Angstroms is at least as great as the peak intensity of the d-spacing maximum at 9.25±0.13 Angstroms. Additionally, the peaks with d-spacing maxima at 11.06±0.18 and 9.25±0.13 Angstroms may be non-discrete peaks.

Further the EMM-10-P relates to a crystalline MCM-22 family molecular sieve that has a total surface area of greater than 450 m2/g as measured by the N2 BET method, and preferably has a ratio of the external surface area over the total surface area of less than 0.15 after conversion into H-form by exchange with ammonium nitrate and calcination, wherein the external surface area is determined from a t-plot of the N2 BET.

Additionally, the EMM-10-P relates to a MCM-22 family crystalline molecular sieve that has a morphology of tabular habit, wherein at least 50 wt % of the crystalline molecular sieve have a crystal diameter greater than 1 μm as measured by the SEM, preferably greater than 2 μm as measured by the SEM, preferably at least 50 wt % of the crystalline molecular sieve have a crystal thickness of about 0.025 μm as measured by the SEM.

U.S. patent application Ser. No. 11/827,953, its entirety of which is enclosed herein by reference, discloses a novel crystalline MCM-22 family molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern including a peak at d-spacing maximum of 12.33±0.23 Angstroms, a distinguishable peak at a d-spacing maximum between 12.57 to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximum between 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacing maximum between 12.57 to about 14.17 Angstroms is less than 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms.

The EMM-10-P as disclosed in U.S. patent application Ser. No. 11/827,953, may be made by crystallizing a mixture having a composition in molar ratio listed in Table 3.

TABLE 3
Reactants Useful Preferred
YO2/X2O3 10 to infinity 15-55
H2O/YO2 1 to 10000  5-35
OH/YO2* 0.001-0.39  0.1-0.35
OH/YO2** 0.001-0.59 0.1-0.5
M/YO2 0.001-2   0.1-1  
R/YO2 0.001-2   0.01-0.5 
Seed*** 0-25 wt % 1-5 wt %
R Me6-diquat-5 salt(s) Me6-diquat-5 salt(s)

After crystallization, the EMM-10-P product has a composition in molar ratio listed in Table 4.

TABLE 4
Reactants Useful Preferred
YO2/X2O3 10 to infinity
M/X2O3 0.005-0.1
R/X2O3  1-4
R Me6-diquat-5 salt(s) Me6-diquat-5 salt(s)

U.S. patent application Ser. No. 11/827,953, its entirety of which is enclosed herein by reference, discloses a novel crystalline MCM-22 family molecular sieve. The as-synthesized composition disclosed in U.S. patent application Ser. No. 11/827,953 is a novel crystalline MCM-22 family molecular sieve having, in its as-synthesized form, an X-ray diffraction pattern including a peak at d-spacing maximum of 12.33±0.23 Angstroms, a distinguishable peak at a d-spacing maximum between 12.57 to about 14.17 Angstroms and a non-discrete peak at a d-spacing maximum between 8.8 to 11 Angstroms, wherein the peak intensity of the d-spacing maximum between 12.57 to about 14.17 Angstroms is less than 90% of the peak intensity of the d-spacing maximum at 12.33±0.23 Angstroms. The as-synthesized composition of U.S. patent application Ser. No. 11/827,953 may further comprises XRD peaks at d-spacing maxima at 3.57±0.06 and 3.43±0.06 Angstroms and/or a d-spacing maximum at 28±1 Angstroms.

Furthermore, the X-ray diffraction pattern of the as-synthesized composition of U.S. patent application Ser. No. 11/827,953 includes values and relative intensities substantially as shown in Table 5:

TABLE 5
Interplanar d-Spacing (Å) Relative Intensity, I/Io × 100
14.17 > d > 12.57 M-VS
12.33 ± 0.23  M-VS
11.1 to 8.8 W-S
4.41 ± 0.1  W-M, broad
3.96 ± 0.08 W-VS, broad
3.57 ± 0.06 W-M
3.43 ± 0.06 M-VS

The solid content of an EMM-10-P family composition used in the weight ratio of the solid content of the EMM-10-P family composition over the acidic composition and the weight ratio of the spacing agent over the solid content of the EMM-10-P family composition is calculated by the total weight of tetravalent element oxide and trivalent element oxide in an EMM-10-P family composition.

(2) Acidic Compositions

The acidic composition useful for this disclosure comprises an acidic solute and a solvent. The acidic solute comprises at least one of inorganic acid, such as, nitric acid hydrochloric acid and sulfuric acid, and organic acid, such as, oxalic acid and acetic acid, or any combination of inorganic acid and organic acid. Preferably, the acidic solute is nitric acid. The solvent comprises at least one of water, methanol, ethanol, acetone and dimethylsulfone (DMSO).

The acid concentration of the acidic composition is in the range of 0.001 to 10. The following acid concentrations are useful lower limits: 0.001, 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, and 9. The following acid concentrations are useful upper limits: 0.01, 0.05, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. The acid concentration falls in a range between any one of the above-mentioned lower limits and any one of the above-mentioned upper limits, so long as the lower limit is less than or equal to the upper limit. The acid concentration may be present in an amount ranging from 0.001 to 5 in one embodiment, alternatively 0.01 to 4, and alternatively 0.1 to 2.

The weight of acidic composition as used in the solid content over acidic composition weight ratios is calculated based on the total weight of acidic solute and solvent.

(3) Optional Spacing Agent

Optionally, the acidic treatment step also comprises a spacing agent. The spacing agent useful is any agent capable of providing a silicon moiety that can stabilize the precursor in expanded form (i.e. having the distinct (002) peak at 13.5±0.25 in both as-synthesized and calcined forms).

Examples of compounds for spacing include organo-compounds of a tetravalent element, a trivalent element, and/or pentavalent compounds, such as, organosilicon compound, organogermanium compound, orgnotitanium compounds, organoboron compounds, organoaluminum compound, and organophorphous compound. The organosilicon silicon compounds may comprise a polysiloxane include silicones, a siloxane, and a silane including disilanes and alkoxysilanes.

Silicone compounds that can be used in the present invention include the following: wherein R1 is hydrogen, fluoride, hydroxy, alkyl, aralkyl, alkaryl or fluoro-alkyl. The


hydrocarbon substituents generally contain from 1 to about 10 carbon atoms and preferably are methyl or ethyl groups. R2 is selected from the same group as R1, and n is an integer of at least 2 and generally in the range of 2 to about 1000. The molecular weight of the silicone compound employed is generally between about 80 to about 20,000 and preferably about 150 to about 10,000. Representative silicone compounds include dimethylsilicone, diethylsilicone, phenylmethylsilicone, methyl hydrogensilicone, ethylhydrogensilicone, phenylhydrogensilicone, fluoropropylsilicone, ethyltrifluoroprophysilicone, tetrachlorophenyl methyl methylethylsilicone, phenylethylsilicone, diphenylsilicone, methyltrisilicone, tetrachlorophenylethyl silicone, methylvinylsilicone and ethylvinylsilicone. The silicone compound need not be linear but may be cyclic as for example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, hexaphenyl cyclotrisiloxane and octaphenylcyclotetrasiloxane. Mixtures of these compounds may also be used as well as silicones with other functional groups.

Useful siloxanes and polysiloxanes include as non-limiting example hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethyl cyclopentasiloxane, hexamethyldisiloxane, octamethylrisiloxane, decamethyltetrasiloxane, hexaethylcyclotrisiloxane, octaethylcyclo tetrasiloxane, hexaphenylcyclotrisiloxane and octaphenylcyclo-tetrasiloxane.

Useful silanes, disilanes, or alkoxysilanes include organic substituted silanes having the general formula:


wherein R is a reactive group such as hydrogen, alkoxy, halogen, carboxy, amino, acetamide, trialkylsilyoxy, R1, R2 and R3 can be the same as R or can be an organic radical which may include alkyl of from 1 to about 40 carbon atoms, alkyl or aryl carboxylic acid wherein the organic portion of alkyl contains 1 to about 30 carbon atoms and the aryl group contains about 6 to about 24 carbons which may be further substituted, alkylaryl and arylalkyl groups containing about 7 to about 30 carbon atoms. Preferably, the alkyl group for an alkyl silane is between about 1 and about 4 carbon atoms in chain length. Mixtures may also be used.

The silanes or disilanes include, as non-limiting examples, dimethylphenylsilane, phenytrimethylsilane, triethylsilane and hexamethyldislane. Useful alkoxysilanes are those with at least one silicon-hydrogen bond.

Molecular Sieve Preparation

A summary of the molecular sieves and/or zeolites, in terms of production, modification and characterization of molecular sieves, is described in the book “Molecular Sieves—Principles of Synthesis and Identification”; (R. Szostak, Blackie Academic & Professional, London, 1998, Second Edition). In addition to molecular sieves, amorphous materials, chiefly silica, aluminum silicate and aluminum oxide, have been used as adsorbents and catalyst supports. A number of long-known forming techniques, like spray drying, pilling, pelletizing and extrusion, have been and are being used to produce macrostructures in the form of, for example, spherical particles, extrudates, pellets and Tablets of both micropores and other types of porous materials for use in catalysis, adsorption and ion exchange. A summary of these techniques is described in “Catalyst Manufacture,” A. B. Stiles and T. A. Koch, Marcel Dekker, New York, 1995.

To the extent desired, the original metal cations of the as-synthesized material can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations. Preferred replacing cations include metal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions and mixtures thereof. Particularly preferred cations are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups 1-17, preferably Groups 2-12 of the Periodic Table of the Elements.

The EMM-12 crystalline molecular sieve of this disclosure should be generally dehydrated, at least partially. This can be done by heating to a temperature in the range of e.g., 200° C. to 595° C. in an atmosphere such as air or nitrogen, and at atmospheric, sub-atmospheric or super-atmospheric pressures for e.g., between 30 minutes and 48 hours. The degree of dehydration is measured by the percentage of weight loss relative to the total weight loss of a molecular sieve sample at 595° C. under flowing dry nitrogen (less than 0.001 kPa partial pressure of water vapor) for 48 hours. Dehydration can also be performed at room temperature (˜25° C.) merely by placing the silicate in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.

The EMM-12 crystalline molecular sieve of this disclosure especially in its metal, hydrogen and ammonium forms can be beneficially converted to another form by thermal treatment. This thermal treatment is generally performed by heating one of these forms at a temperature of at least 370° C. for at least one minute and generally not longer than 1000 hours. While sub-atmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment can be performed at a temperature up to about 925° C. The thermal treated product is particularly useful in the catalysis of certain hydrocarbon conversion reactions. The thermally treated product, especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic, e.g., hydrocarbon, conversion reactions. Non-limiting examples of such reactions include those described in U.S. Pat. Nos. 4,954,325; 4,973,784; 4,992,611; 4,956,514; 4,962,250; 4,982,033; 4,962,257; 4,962,256; 4,992,606; 4,954,663; 4,992,615; 4,983,276; 4,982,040; 4,962,239; 4,968,402; 5,000,839; 5,001,296; 4,986,894; 5,001,295; 5,001,283; 5,012,033; 5,019,670; 5,019,665; 5,019,664; and 5,013,422, each incorporated herein by reference as to the description of the catalytic reactions.

The EMM-12 crystalline molecular sieve of this disclosure can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.

It is desired to incorporate the EMM-12 molecular sieve with another material resistant to the temperatures and other conditions employed in alkylation processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the EMM-12 molecular sieve, i.e. combined therewith or present during synthesis of the EMM-12 molecular sieve, which is active, tends to change the conversion and/or selectivity of the catalyst. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained economically and orderly without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. The materials, i.e. clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay binders have been employed normally only for the purpose of improving the crush strength of the catalyst.

Naturally occurring clays which can be composited with the EMM-12 molecular sieve include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dictite, narcite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, notably alumina.

In addition to the foregoing materials, the EMM-12 molecular sieve can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia silica-alumina-magnesia and silica-magnesia-zirconia.

The relative proportions of finely divided EMM-12 crystalline molecular sieve and inorganic oxide matrix vary widely, with the crystal content ranging from about 1 to about 99 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 20 to about 80 wt % of the composite.

The following examples reflect embodiments of the invention and are by no means intended to be limiting of the scope of the invention.

Experiments Powder X-Ray Diffraction

Powder x-ray data were obtained on a Bruker D4 instrument in Bragg-Brentano geometry with monochromatic Cu Kα radiation. The pattern used for structural characterization extended from 1.2 to 80° in 20. Intensities for Rietveld refinement were extracted from the continuous scans.

Surface Areas

The overall surface area of a molecular sieve may be measured by the Brunauer-Emmett-Teller (BET) method using adsorption-desorption of nitrogen (temperature of liquid nitrogen, 77 K). The internal surface area may be calculated using t-plot of the Brunauer-Emmett-Teller (BET) measurement. The external surface area is calculated by subtracting the internal surface area from the overall surface area measured by the Brunauer-Emmett-Teller (BET) measurement.

Collidine Number Measurement

The collidine number of a molecular sieve may be measured by TGA. A sample is dried at 200° C. to constant weight (weight change less than ±1% for the period of 1 hour). The weight of the dried sample, the sorbate, is then measured. The sorbent, 2,4,6-collidine, is delivered by a sparger maintained at 3 Torr collidine partial pressure and carried over the sample by nitrogen passed 200 ml/min for 60 min. The collidine number is expressed as micromoles of adsorbed per gram of the sorbate.

Example 1 Preparation of EMM-12

A sample of EMM-10-P (3 g) made according to Example 1 of U.S. patent application Ser. No. 11/823,129 was added to the mixture of 30 g of 1 M nitric acid and 0.5 g of diethoxydimethylsilane. The reaction was carried out in a teflon container sealed in a Parr™ bomb in the oven at 170° C. for 24 hrs. The solid product of EMM-12 was isolated by filtration, washed and dried at 120° C.

The XRD pattern of the solid product of EMM-12 is characterized as comprising a doublet at between 12.45 and 13.60 Angstroms, corresponding to 6.5-7.1° 2θ (Cu Kα) and non-discrete scattering between 8.85 to 11.05 Angstroms, the 8-10° 2θ (Cu Kα) region or exhibit a valley in between the peaks at 11.05±0.18 and 9.31±0.13 Angstroms but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

The calcined product of EMM-12 has high surface area of 575 m2/g and collidine adsorption of 343 μmoles/g.

Example 2 Preparation of EMM-12

A sample of EMM-10-P (3 g) made according to Example 1 of U.S. patent application Ser. No. 11/823,129 was added to the mixture of 30 g of 1 M nitric acid. The reaction was carried out in a teflon container sealed in a Parr™ bomb in the oven at 170° C. for 24 hrs. The solid product of EMM-12 was isolated by filtration, washed and dried at 120° C.

The XRD pattern of the solid product of EMM-12 is characterized as comprising a doublet at between 12.45 and 13.60 Angstroms, corresponding to 6.5-7.1° 2θ (Cu Kα) and non-discrete scattering between 8.85 to 11.05 Angstroms, the 8-10° 2θ (Cu Kα) region or exhibit a valley in between the peaks at 11.05±0.18 and 9.31±0.13 Angstroms but with measured intensity corrected for background at the lowest point being not less than 50% of the point at the same XRD d-spacing on the line connecting maxima at around 11.05±0.18 and 9.31±0.13 Angstroms.

The calcined product of EMM-12 has high surface area of 471 m2/g and collidine adsorption of 60 μmoles/g.

Example 3

The filtered, washed and dried samples of Examples 1 and 2 were combined, exchanged with 1 N ammonium nitrate and calcined at 540° C. in air to convert the composite sample to the H-form of EMM-12.

Benzene

Benzene was obtained from a commercial source. The benzene was passed through a pretreatment vessel containing equal parts (by volume) molecular sieve 13X, molecular sieve 4A, Engelhard F-24 Clay, and Selexsorb CD (in order from inlet to outlet), and then through a pretreatment vessel containing MCM-22 catalyst. All feed pretreatment materials were dried in a 260° C. oven for 12 hours before using.

Nitrogen

Nitrogen was ultra high purity grade and obtained from a commercial specialty gases source.

Example 4 Preparation of the Metal Containing Inorganic Oxide

A commercially available gamma-alumina (Catalox™ HTA-101) was slurried in water with a commercially available palladium salt (target 0.6 wt. % Pd), dried overnight at 121° C. followed by calcination at 538° C. in air to convert the palladium salt to palladium oxide. The palladium containing alumina was milled to less than 10 microns.

Example 5 Benzene Hydroalkylation

A 41 wt % EMM-12 calcined of Example 3 and 59 wt % palladium-containing alumina catalyst of Example 4 was prepared. This catalyst was tested for benzene hydroalkylation to form cyclohexylbenzene.

Feed Pretreatment The experiment was conducted in a fixed bed ⅜″ OD tubular reactor in a downflow configuration with an ⅛″ internal thermocouple. The reactor furnace was controlled in isothermal mode. Two grams of catalyst sized to 14/25 mesh was loaded into the ⅜″ reactor. Experiment was conducted with catalyst as 14/25 mesh loaded into the ⅜″ reactor. The catalyst bed was axially centered in the middle furnace zone. The catalyst was packed with inert sand to fill the interstitial void spaces. Reaction conditions were 156° C., 1076 kPa-g and the hydrogen to benzene molar ratio was 0.69. Weight hourly space velocity was 1.05 hr−1 on a benzene basis.

The benzene conversion was approximately 37%, and the cyclohexylbenzene to di-cyclohexylbenzene (weight) ratio was approximately 88.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3197399Oct 15, 1962Jul 27, 1965Union Oil Company Of CalifornaHydrocracking catalyst activation
US3201356Sep 27, 1961Aug 17, 1965Exxon Research Engineering CoMolecular sieve catalyst activation process
US3347945Oct 21, 1965Oct 17, 1967Shell Oil CoHydrodimerization of benzene
US3390101Mar 23, 1966Jun 25, 1968Chevron ResCatalyst activation process
US3412165Feb 15, 1967Nov 19, 1968Shell Oil CoPhenylcyclohexane process
US3536771Feb 7, 1969Oct 27, 1970Universal Oil Prod CoMethod for producing cyclohexane via the hydrogenation of benzene
US3751504May 12, 1972Aug 7, 1973Mobil Oil CorpVapor-phase alkylation in presence of crystalline aluminosilicate catalyst with separate transalkylation
US3760017May 17, 1971Sep 18, 1973Texaco IncHydroalkylation catalyst and process
US3760018May 17, 1971Sep 18, 1973Texaco IncHydroalkylation catalyst and process
US3760019May 17, 1971Sep 18, 1973Texaco IncHydroalkylation catalyst and process
US3784617Dec 6, 1972Jan 8, 1974Arkell AHydroalkylation of mononuclear aromatic hydrocarbons
US3784618Aug 25, 1972Jan 8, 1974Texaco IncHydroalkylation process
US3839477Jun 6, 1973Oct 1, 1974Texaco IncHydroalkylation process
US3864421May 7, 1973Feb 4, 1975Texaco IncHydroalkylation of aromatic hydrocarbons
US3957687Dec 4, 1972May 18, 1976Texaco Inc.Group viii metal on an acidic oxide support
US3962362Mar 31, 1975Jun 8, 1976Texaco Development CorporationMethod for preparing polyphenyls
US4016218May 29, 1975Apr 5, 1977Mobil Oil CorporationAlkylation in presence of thermally modified crystalline aluminosilicate catalyst
US4021490Oct 14, 1975May 3, 1977Phillips Petroleum CompanyProcess for production of phenol and cyclohexanone
US4094918Feb 10, 1977Jun 13, 1978Phillips Petroleum CompanyProduction of cycloalkyl aromatic hydrocarbons
US4122125Nov 8, 1976Oct 24, 1978Phillips Petroleum CompanyAromatic hydrocarbons
US4152362Jan 3, 1978May 1, 1979Phillips Petroleum CompanyHydroalkylation using a rhenium, nickel, rare earth zeolite
US4177165Dec 28, 1977Dec 4, 1979Phillips Petroleum CompanyHydroalkylation composition and process for producing said composition
US4206082Aug 23, 1978Jun 3, 1980Phillips Petroleum CompanyRare earth zeolite impregnated with a ruthenium and a nickel compound
US4219687Jul 26, 1978Aug 26, 1980Standard Oil CompanyHydroalkylation of benzene and analogs
US4219689Sep 8, 1978Aug 26, 1980Phillips Petroleum CompanyAromatic hydroalkylation catalyst using iridium on zeolites
US4268699Dec 7, 1979May 19, 1981Phillips Petroleum CompanyHydroalkylation using nickel-ruthenium catalyst on zeolite type support
US4329531May 29, 1980May 11, 1982Phillips Petroleum CompanyRare earth exchanged zeolites
US4380683Dec 22, 1981Apr 19, 1983The Standard Oil CompanyHydroalkylation of benzene and analogs
US4439409Apr 13, 1982Mar 27, 1984Bayer AktiengesellschaftCrystalline aluminosilicate PSH-3 and its process of preparation
US4447554Mar 16, 1982May 8, 1984Phillips Petroleum CompanyIon exchanging zeolite with rare earth, nickel or ammonium cations, then calcining
US4547605Sep 28, 1983Oct 15, 1985Mobil Oil CorporationCatalyst for alkylation of aromatic hydrocarbons
US4826667Feb 17, 1987May 2, 1989Chevron Research CompanyAdamantane quaternary ammonium template
US4891458Dec 17, 1987Jan 2, 1990Innes Robert ALiquid phase alkylation or transalkylation process using zeolite beta
US4954325Oct 6, 1988Sep 4, 1990Mobil Oil Corp.Composition of synthetic porous crystalline material, its synthesis and use
US4954663Jan 25, 1990Sep 4, 1990Mobil Oil Corp.Catalysis with zeolite; alkylation
US4956514Jan 8, 1990Sep 11, 1990Mobil Oil Corp.Forming gasoline hydrocarbons from light olefins with zeolite catalysts
US4962239Dec 26, 1989Oct 9, 1990Mobil Oil Corp.Olefin is etherified with alcohol using zeolite catalyst
US4962250Jan 24, 1990Oct 9, 1990Mobile Oil Corp.Containing a group eight metal and has a porous crystalline structure
US4962255Mar 6, 1989Oct 9, 1990Yeda Research & Development Company LimitedUsing selective crystallized borosilicate glass zeolite or alumina-silica catalyst
US4962256Jan 25, 1990Oct 9, 1990Mobil Oil Corp.Process for preparing long chain alkyl aromatic compounds
US4962257Jan 24, 1990Oct 9, 1990Mobil Oil Corp.Process for the catalytic disproportionation of toluene
US4968402Feb 14, 1990Nov 6, 1990Mobil Oil Corp.Process for upgrading hydrocarbons
US4973784Dec 13, 1989Nov 27, 1990Mobil Oil Corp.Process for reducing the durene content of effluent resulting from the catalytic conversion of C1 -C4 oxygenates to gasoline
US4982033Jan 24, 1990Jan 1, 1991Mobil Oil Corp.Zeolite catalyst
US4982040Dec 21, 1989Jan 1, 1991Mobil Oil Corp.Zeolite catalyst
US4983276Jan 29, 1990Jan 8, 1991Mobil Oil Corp.Octane improvement in catalytic cracking and cracking catalyst composition therefor
US4986894Mar 19, 1990Jan 22, 1991Mobil Oil Corp.Dewaxing waxy hydrocarbons with zeolite
US4992606Jan 25, 1990Feb 12, 1991Mobil Oil Corp.Process for preparing short chain alkyl aromatic compounds
US4992611Dec 13, 1989Feb 12, 1991Mobil Oil Corp.Using zeolite catalyst
US4992615Jan 25, 1990Feb 12, 1991Mobil Oil Corp.Isoparaffin-olefin alkylation process
US5000839Feb 14, 1990Mar 19, 1991Mobil Oil Corp.Hydrocracking process for producing a high density jet fuel
US5001283Jan 24, 1990Mar 19, 1991Mobil Oil Corp.Process for preparing aromatic alkanols
US5001295Mar 15, 1990Mar 19, 1991Mobil Oil Corp.Process for preparing dialkylnaphthalene
US5001296Mar 7, 1990Mar 19, 1991Mobil Oil Corp.Catalytic hydrodealkylation of aromatics
US5012033Jan 25, 1990Apr 30, 1991Mobil Oil Corp.Isoparaffin-olefin alkylation process and catalyst composition thereof
US5013422Feb 14, 1990May 7, 1991Mobil Oil Corp.Catalytic hydrocracking process
US5019664Jan 24, 1990May 28, 1991Mobil Oil Corp.Process for the conversion of paraffins to olefins and/or aromatics and low acidity zeolite catalyst therefor
US5019665Apr 18, 1990May 28, 1991Mobil Oil Corp.Shape-selective process for concentrating diamondoid-containing hydrocarbon solvents
US5019670Apr 26, 1990May 28, 1991Mobil Oil CorporationAlkylation of aromatic compound with olefin hydrocarbon oligomer, porous crystalline acidic alkylation catalyst
US5037538Feb 26, 1990Aug 6, 1991Mobil Oil CorporationSegregation of reducing catalyst; no dilution or cracking catalyst; floating hollow sphere support
US5053571Apr 16, 1990Oct 1, 1991Exxon Chemical Patents Inc.Ruthenium and nickel/support on zeolite beta selectivity
US5108969Aug 22, 1990Apr 28, 1992Mobil Oil Corp.Low acidity catalyst for conversion of paraffins to olefins and/or aromatics
US5146024May 20, 1991Sep 8, 1992Phillips Petroleum CompanyHydroalkylation of aromatic hydrocarbons
US5236575Dec 6, 1991Aug 17, 1993Mobil Oil Corp.Synthetic porous crystalline mcm-49, its synthesis and use
US5250277Dec 20, 1991Oct 5, 1993Mobil Oil Corp.Crystalline oxide material
US5292976Apr 27, 1993Mar 8, 1994Mobil Oil CorporationAromatization, hydrodecyclization, catalytic cracking
US5334795Oct 27, 1992Aug 2, 1994Mobil Oil Corp.Production of ethylbenzene
US5362697Apr 26, 1993Nov 8, 1994Mobil Oil Corp.Synthetic layered MCM-56, its synthesis and use
US5384296Aug 16, 1993Jan 24, 1995Mobil Oil CorporationThermally stable noble metal-container zeolite catalyst
US5488194May 16, 1994Jan 30, 1996Mobil Oil Corp.Using catalyst material having been treated with one or more monomeric or polymeric siloxane compounds which decompose to oxide or non-oxide ceramic species
US5554274Oct 19, 1994Sep 10, 1996Mobil Oil CorporationManufacture of improved catalyst
US5557024May 30, 1995Sep 17, 1996Mobil Oil CorporationProcess for preparing short chain alkyl aromatic compounds
US5705729Nov 22, 1995Jan 6, 1998Mobil Oil CorporationZeolite catalyst
US6037513Jul 9, 1998Mar 14, 2000Mobil Oil CorporationHydroalkylation of aromatic hydrocarbons
US6077498Nov 19, 1996Jun 20, 2000Consejo Superior Investigaciones CientificasZeolite ITQ-1
US6133470Jul 28, 1998Oct 17, 2000Mobil Oil CorporationProducing terephthalic acid and/or dimethyl terephthalate; toluene disproportionation conditions with crystalline molecular sieve catalyst to produce an intermediate product, which is oxidized without need for purification
US6489529Jan 24, 2000Dec 3, 2002Exxonmobil Oil CorporationProduction of monocycloalkyl aromatic compounds
US6504070Feb 2, 2001Jan 7, 2003Nippon Mitsubishi Oil CorporationUsing catalyst comprising iridium compound and ligand to selectively position alkyl chain on aromatic ring
US6506953Jan 24, 2000Jan 14, 2003Exxonmobil Oil CorporationZeolite MCC-68,combined with a hydrogenation metal, has activity for the hydroalkylation of aromatic hydrocarbons
US6730625Nov 9, 1999May 4, 2004Exxonmobil Oil CorporationHydroalkylation of aromatic hydrocarbons
US6781025Jul 11, 2001Aug 24, 2004Exxonmobil Chemical Patents Inc.Reactivation of aromatics alkylation catalysts
US6936744Jul 19, 2000Aug 30, 2005Exxonmobil Chemical Patents, Inc.Alkylaromatics production
US6984764May 4, 1999Jan 10, 2006Exxonmobil Oil Corporationalkylating of benzene with ethylene or propylene in the presence of alkylation catalysts selected from zeolites, to form ethylbenzene or cumene; catalysis
US7488861Mar 17, 2005Feb 10, 2009Catalytic Distillation TechnologiesProcess for the co-production of cumene and secondary butyl benzene
US7579511Oct 10, 2008Aug 25, 2009Exxonmobil Research And Engineering CompanyContacting benzene and hydrogen in presence of catalyst under hydroalkylation conditions to form effluent stream of cyclohexylbenzene, cyclohexane, methyl cyclopentane, unreacted benzene; build up of cyclohexane and methyl cyclopentane in recycle streams is reduced and proportion of benzene is increased
US7824277Nov 17, 2006Nov 2, 2010Acushnet CompanyMetal wood club
US7910778Jul 11, 2008Mar 22, 2011Exxonmobil Chemical Patents Inc.Process for producing cyclohexylbenzene
US7959899Jun 27, 2007Jun 14, 2011Exxonmobil Chemical Patents Inc.Molecular sieve composition (EMM-10-P), its method of making, and use for hydrocarbon conversions
US20030083527Mar 22, 2001May 1, 2003Adolf KuhnleMethod for producing aromatic alcohols, especially phenol
US20040092757Oct 27, 2003May 13, 2004Showa Denko K.K.Crystalline MWW-type titanosilicate catalyst for producing oxidized compound, production process for the catalyst, and process for producing oxidized compound by using the catalyst
US20050158238Feb 26, 2003Jul 21, 2005Takashi TatsumiMww type zeolite substance, precursor substance therefor, and process for producing these substances
US20080027256Jul 2, 2007Jan 31, 2008Roth Wieslaw JMolecular sieve composition (EMM-10), its method of making, and use for hydrocarbon conversions
US20080027259Jun 27, 2007Jan 31, 2008Roth Wieslaw JMolecular sieve composition (EMM-10-P), its method of making, and use for hydrocarbon conversions
US20080045768Jul 13, 2007Feb 21, 2008Roth Wieslaw Jcrystalline MCM-22 family molecular sieve containing mixed oxide of silicon, aluminum, alkali or alkaline metal oxide, water, N,N,N,N'N'N'-hexamethyl-1,5pentanediaminium salt(s), N,N,N,N'N'N'-hexamethyl-1,6-hexanediaminium salt as catalyst template; crystallization; catalyst for hexane cracking
US20110037022Mar 16, 2009Feb 17, 2011Exxonmobil Chemical Patents Inc.Process for Producing Phenol and/or Cyclohexanone
EP0293032A2May 11, 1988Nov 30, 1988ENIRICERCHE S.p.A.Synthetic, crystalline, porous material containing oxides of silicon and boron
EP0338734A2Apr 14, 1989Oct 25, 1989Exxon Chemical Patents Inc.Reductive alkylation process
JP2005342644A Title not available
WO1995031421A1May 11, 1995Nov 23, 1995Mobil Oil CorpSelective production of para-dialkyl substituted benzenes
Non-Patent Citations
Reference
1"Periodic Table of the Elements", Chemical and Engineering News, vol. 63, No. 5, pp. 27 (1995).
2C. Baerlocher et al., "Charge Flipping Combined With Histogram Matching To Solve Complex Crystal Structures From Powder Diffraction Data", Z. Kristallogr., vol. 222, pp. 47-53 (2007).
3C. Gilmore et al., "A Multisolution Method Of Phase Determination By Combined Maximization Of Entropy And Likelihood, II. Application To Small Molecules", Acta Cryst., A46, pp. 297-308 (1990).
4C. Gilmore et al., "A Multisolution Method Of Phase Determination By Combined Maximization Of Entropy And Likelihood, VI. The Use of Error-Correcting Codes As A Source Of Phase Problem In Powder, Electron And Macromolecular Crystallography", Acta Cryst., A55, pp. 70-83 (1990).
5C. Gilmore et al., "Applications of the Maximum Entropy Method to Powder Diffraction and Electron Crystallography", Proc. R. Soc., London, vol. 442, pp. 97-111 (1993).
6I. Borodina et al., "Hydroalkylation of Benzene and Ethylbenzene over Metal Containing Zeolite Catalysts", Microporous and Mesoporous Materials, 2007, vol. 105, pp. 181-188.
7J. Raun et al., "Structure Investigation of Novel 3-D Crystalline Silicates From Layered Precursors," 15 IZC Conference, Beijing, Book of Abstracts (2007).
8J. Ruan et al., "Structure Elucidation of the Highly Active Titanosilicate Catalyst Ti-YNU-1", Angew. Chem. Int. Ed., 2005, vol. 44, pp. 6719-6723.
9L. Slaugh et al., "Hydrodimerization of Benzene to Phenylcyclohexane over Supported Transition Metal Catalysts", Journal of Catalysis, 1969, vol. 13, pp. 385-396.
10L. Zhicheng et al., "Static Synthesis of High-Quality MCM-22 Zeolite with High SiO2/A12O3 Ratio", Chinese Science Bull, 2004, vol. 49, No. 6, pp. 556-561.
11Meier et al., "Atlas of Zeolite Framework Types", Elsevier, Fifth Edition, 2001.
12P. Wu et al., "Methodology for Synthesizing Crystalline Metallosilicates with Expanded Pore Windows Through Molecular Alkoxysilylation of Zeolitic Lamellar Precursors" , Journal of American Chemical Soc., 2008, vol. 130, pp. 8178-8187.
13R. Vincent et al., "Double Conical Beam-Rocking System For Measurement Of Integrated Electron Diffraction Intensities", Ultramicroscopy, vol. 53, pp. 271-282 (1994).
14R. Young, "The Rietveld Method", Oxford Univ. Press, Oxford, pp. 11 (1995).
15S. Hovmoller et al., "CRISP: Crystallographic Image Processing On A Personal Computer", Ultramicroscopy, vol. 41, pp, 121-135 (1992).
16S. Kim et al., "Structural Evolution of B-MCM-36 and B-ITQ-2 from B-MCM-22", Bull. Korean Chem. Society, 2006, vol. 27, No. 10, pp. 1693-1696.
17S. Lawton et al., "Zeolite MCM-49: A Three-Dimensional MCM-22 Analogue Synthesized by in Situ Crystallization", Journal of Physical Chemistry, 1996, vol. 100, pp. 3788-3798.
18S. Maheshwari et al., "Layer Structure Preservation During Swelling, Pillaring, and Exfoliation of a Zeolite Precursor", Journal of American Chemical Soc., 2008, vol. 130, pp. 1507-1516.
19W. Fan et al., "A Titanosilicate That Is Structurally Analogous To An MWW-Type Lamellar Precursor", Angew. Chem. Int. Ed., vol. 43, pp. 236-240 (2004).
20W. Fan et al., "Synthesis and Catalytic Properties of a New Titanosilicate Molecular Sieve with the Structure Analogous to MWW-type Lamellar Precursor", Journal of Catalyst, 2006, vol. 243, pp. 183-191.
21Z. Liu et al., "Static Synthesis of High-Quality MCM-22 Zeolite With High Si02/A1203 Ratio", Chinese Science Bulletin, vol. 49, No. 6, pp. 556-561 (2004).
Classifications
U.S. Classification585/467
International ClassificationC07C2/58
Cooperative ClassificationB01J29/7276, B01J29/7038, C01B39/48, B01J29/7676, B01J29/7476, C01B39/46
European ClassificationB01J29/74L, B01J29/70L, B01J29/76L, C01B39/46, B01J29/72L, C01B39/48
Legal Events
DateCodeEventDescription
Nov 23, 2010ASAssignment
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ROTH, WIESLAW J.;HELTON, TERRY E.;CHENG, JANE C.;AND OTHERS;SIGNING DATES FROM 20101111 TO 20101115;REEL/FRAME:025398/0903
Owner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXAS